Classifications

• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
  • G03G9/00—Developers
  • G03G9/08—Developers with toner particles
  • G03G9/087—Binders for toner particles
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
  • G03G9/00—Developers
  • G03G9/08—Developers with toner particles
  • G03G9/087—Binders for toner particles
  • G03G9/08702—Binders for toner particles comprising macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
  • G03G9/0874—Polymers comprising hetero rings in the side chains
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/40—High-molecular-weight compounds
  • C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J3/00—Processes of treating or compounding macromolecular substances
  • C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/04—Oxygen-containing compounds
  • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
  • C08K5/098—Metal salts of carboxylic acids
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
  • C08L25/02—Homopolymers or copolymers of hydrocarbons
  • C08L25/04—Homopolymers or copolymers of styrene
  • C08L25/08—Copolymers of styrene
  • C08L25/14—Copolymers of styrene with unsaturated esters
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
  • C08L33/04—Homopolymers or copolymers of esters
  • C08L33/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur, or oxygen atoms in addition to the carboxy oxygen
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
  • G03G9/00—Developers
  • G03G9/08—Developers with toner particles
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
  • G03G9/00—Developers
  • G03G9/08—Developers with toner particles
  • G03G9/0802—Preparation methods
  • G03G9/081—Preparation methods by mixing the toner components in a liquefied state; melt kneading; reactive mixing
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
  • G03G9/00—Developers
  • G03G9/08—Developers with toner particles
  • G03G9/087—Binders for toner particles
  • G03G9/08702—Binders for toner particles comprising macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
  • G03G9/08704—Polyalkenes
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
  • G03G9/00—Developers
  • G03G9/08—Developers with toner particles
  • G03G9/09—Colouring agents for toner particles
  • G03G9/0902—Inorganic compounds
  • G03G9/0904—Carbon black
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
  • G03G9/00—Developers
  • G03G9/08—Developers with toner particles
  • G03G9/097—Plasticisers; Charge controlling agents
  • G03G9/09783—Organo-metallic compounds
  • G03G9/09791—Metallic soaps of higher carboxylic acids

Definitions

• the present invention relates to a binder resin for toner and a toner.
• an electrophotographic method in a Plain Paper Copy (PPC) copying machine or a printer in which a toner image formed on a photoreceptor is transferred onto a recording paper is performed by a procedure as follows. First, an electrostatic latent image is formed on the photoreceptor. Next, after the latent image is developed by using a toner and the toner image is transferred onto a sheet to be fixed such as a paper, the toner image is fixed by heating with a heat roll or a film. In this method, since fixing is performed under heating in a state in which the toner on the sheet to be fixed directly comes into contact with a heat roll or a film, fixing is promptly performed and a thermal efficiency is extremely excellent. Therefore, a fixing efficiency is very good.
• PPC Plain Paper Copy
• a binder resin in which a resin having a high molecular weight and a resin having a low molecular weight are mixed to be used and a high molecular weight part is crosslinked (for example, WO 2008/075463 , WO 2009/028177 , JP-A-2000-235279 , JP-A-2005-266788 , WO 2004/015498 , JP-A-2006-171364 and WO 2011/061917 ).
• EP-A-2 602 664 discloses a binder resin for a toner containing a vinyl resin (A), a non-crystalline polyester resin (SN) and a saturated crystalline polyester resin (SC), wherein (A) is composed of a carboxyl group-containing vinyl resin (C), a glycidyl group-containing vinyl resin (E) and a reaction product of the vinyl resins,and the content od (A) is 65-95 wt.-%, based on the total of (A), (SN) and (SC), the ester group concentration of (SC) is 10.0-13.5 mmol/g, (SN) is dispersed in an island form in (A) and (SC) is contained in the island phase of (SN), and a metal component (M) containing at least one of Zn, Ca, Mg, Al and Ba (but excluding metal oxide) is contained at least (SC).
• A is composed of a carboxyl group-containing vinyl resin (C), a glycidyl group-containing vinyl resin
• EP-A-2 503 394 describes a binder resin for a toner containing at least a carboxyl group-containing vinyl resin (C), a glycidyl group-containing vinyl resin (E), a reaction product of the vinyl resins and a saturated crystalline polyester (S), wherein (S) has a predetermined melting point and a predetermined metal component (M), and the binder resin for a toner has a predetermined loss modulus (G") and a predetermined storage modulus (G').
• the present invention is to solve a problem in which such a toner in the related art has and to provide a binder resin for toner and a toner excellent in a balance among fixing properties, offset resistance, durability, and toner productivity.
• the present invention provides a resin suitable as a binder resin for toner, containing
• a toner comprising the binder resin of the present invention and a coloring agent.
• the invention provides a method of manufacturing a resin suitable as a binder resin for toner, comprising performing a crosslinking reaction by melting and kneading
• a binder resin for toner and a toner excellent in a balance among fixing properties, offset resistance, durability, and toner productivity.
• polymerization may be used for the meaning of copolymerization, and the term “polymer” may be used for the meaning of a copolymer.
• polymer may be used for the meaning of a copolymer.
• to indicates that both the upper limit value and the lower limit value are included otherwise specifically mentioned.
• parts by mass is abbreviated as “pbm”
• GPC gel permeation chromatography
• peak indicates a main peak
• a binder resin for toner in the present invention contains a carboxy group-containing vinyl resin (C), a glycidyl group-containing vinyl resin (E), a reactant thereof, and a fatty acid metal salt (M).
• the binder resin for toner in the present invention is one in which the reactant of the carboxy group-containing vinyl resin (C) and the glycidyl group-containing vinyl resin (E) is formed in the presence of the fatty acid metal salt (M), and contains the fatty acid metal salt (M) of the formula (C n H 2 n +1 COO) m -M (1) wherein n is an integer of 11-22, m is 2, and M is a metal atom selected from Zn and Ca.
• the fatty acid metal salt (M) is dispersed at least in the binder resin for toner and a slipping effect is not intended by the fatty acid metal salt (M)
• the fatty acid metal salt (M) is not segregated on the surface layer of the toner unlike as a fatty acid metal salt included in an external additive such as a lubricant.
• the existence of the fatty acid metal salt (M) according to the present invention in the binder resin for toner can be confirmed by the following method. That is, in a case of the binder resin for toner, it is possible to confirm by performing a scanning electron microscope (SEM) at a magnification from 1,000-5,000 times/X-ray microanalyzer (XMA) mapping analysis after trimming and surface shaping. In a case of the toner, firstly, after the toner is embedded in e.g. an epoxy resin, it is possible to confirm by the same operation as that of the binder resin. On the other hand, segregation of a metal included in an external additive on the surface layer of the toner can be confirmed by performing a scanning electron microscope (SEM)/X-ray microanalyzer (XMA) mapping analysis.
• SEM scanning electron microscope
• XMA X-ray microanalyzer
• the fatty acid metal salt (M) in the present invention for example, a Zn salt and a Ca salt of lauric acid, myristic acid, palmitic acid, stearic acid, and behenic acid are included, and zinc stearate and calcium stearate are particularly preferable.
• the content of the fatty acid metal salt (M) in the present invention is preferably 0.001-3 pbm, more preferably 0.05-2 pbm, and further preferably 0.1-1 pbm, with respect to 100 pbm of the total amount of the carboxy group-containing vinyl resin (C) and the glycidyl group-containing vinyl resin (E), from the viewpoint of a balance between offset resistance and durability.
• the fatty acid metal salt (M) acts as a catalyst in the reaction of the carboxy group-containing vinyl resin (C) with the glycidyl group-containing vinyl resin (E).
• the binder resin for toner to have an appropriate viscosity by reacting the carboxy group-containing vinyl resin (C) with the glycidyl group-containing vinyl resin (E) in the presence of the fatty acid metal salt (M) which acts as a reactive catalyst.
• the content of the fatty acid metal salt (M) is equal to or more than 0.001 pbm, the reaction of the carboxy group-containing vinyl resin (C) with the glycidyl group-containing vinyl resin (E) becomes excellent and the viscosity of the binder resin increases, and as a result, it is possible to more improve offset resistance.
• the content of the fatty acid metal salt (M) is equal to or less than 3 pbm, it is possible to obtain the toner having more excellent storage stability and durability.
• the fatty acid metal salt (M) may be added at any stage of steps of manufacturing the binder resin for toner. It is possible to add the fatty acid metal salt (M) when the carboxy group-containing vinyl resin (C) is manufactured or to add the fatty acid metal salt (M) when the carboxy group-containing vinyl resin (C) reacts with the glycidyl group-containing vinyl resin (E) described below, furthermore, it is possible to combine these addition methods. In addition, it is also possible to add the fatty acid metal salt (M) when the binder resin is manufactured, and further, to add it when the toner is manufactured.
• the carboxy group-containing vinyl resin (C) preferably includes the high molecular weight vinyl resin (H) having a peak in a region in which the molecular weight is equal to or more than 2.5 ⁇ 10 4 and equal to or less than 1.2 ⁇ 10 5 in the molecular weight distribution of the THF soluble content measured by GPC and the low molecular weight vinyl resin (L) having a peak in a region in which the molecular weight is equal to or more than 2 ⁇ 10 3 and equal to or less than 2 ⁇ 10 4 in the molecular weight distribution of the THF soluble content measured by GPC.
• the mass ratio (H/L) of the high molecular weight vinyl resin (H) to the low molecular weight vinyl resin (L) in the carboxy group-containing vinyl resin (C) is preferably 55/45 to 85/15, and the ratio (H/L) is more preferably 60/40 to 80/20 and further preferably 60/40 to 75/25, from the viewpoint of the total balance among fixing properties, offset resistance, and durability of the toner.
• the molecular weight distribution (Mw/Mn) is preferably 6-15. By setting the molecular weight distribution to this range, it is possible to obtain the toner having a more excellent balance among fixing properties, offset resistance, and productivity.
• a monomer configuring the carboxy group-containing vinyl resin (C) As a monomer configuring the carboxy group-containing vinyl resin (C), a styrene-based monomer, and an acryl-based monomer (also including a methacryl-based monomer, hereinafter the same) are included in addition to a carboxy group-containing monomer.
• styrene-based monomer used in the present invention for example, styrene, p-methylstyrene, m-methylstyrene, o-methylstyrene, p-methoxystyrene, p-phenylstyrene, p-chlorostyrene, 3,4-dichlorostyrene, p-ethylstyrene, 2,4-dimethylstyrene, p-n-butylstyrene, p-tert-butylstyrene, p-n-hexylstyrene, p-n-octylstyrene, p-n-nonylstyrene, p-n-decylstyrene, and p-n-dodecylstyrene are included, and styrene is particularly preferable.
• acrylic acid esters such as methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, octyl acrylate, cyclohexyl acrylate, stearyl acrylate, benzyl acrylate, furfuryl acrylate, hydroxyethyl acrylate, hydroxybutyl acrylate, dimethylaminomethyl acrylate, or dimethylaminoethyl acrylate, methacrylic acid esters such as methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, octyl methacrylate, cyclohexyl methacrylate, stearyl methacrylate, benzyl methacrylate, furfuryl methacrylate, hydroxyethyl methacrylate, hydroxybutyl methacrylate, dimethyl
• acrylic acid esters, methacrylic acid esters, acrylonitrile, and methacrylonitrile are preferable, and butyl acrylate, methyl methacrylate, butyl methacrylate, and hydroxyethyl acrylate are more preferable.
• diesters of an unsaturated dibasic acid such as dimethyl fumarate, dibutyl fumarate, dioctyl fumarate, dimethyl maleate, dibutyl maleate, or dioctyl maleate can also be used as a monomer in addition to the monomers describe above.
• carboxy group-containing monomer used in the present invention for example, monoesters of an unsaturated dibasic acid such as acrylic acid, methacrylic acid, maleic acid anhydride, maleic acid, fumaric acid, cinnamic acid, methyl fumarate, ethyl fumarate, propyl fumarate, butyl fumarate, octyl fumarate, methyl maleate, ethyl maleate, propyl maleate, butyl maleate, or octyl maleate are included.
• an unsaturated dibasic acid such as acrylic acid, methacrylic acid, maleic acid anhydride, maleic acid, fumaric acid, cinnamic acid, methyl fumarate, ethyl fumarate, propyl fumarate, butyl fumarate, octyl fumarate, methyl maleate, ethyl maleate, propyl maleate, butyl maleate, or octyl
• Acrylic acid, methacrylic acid, fumaric acid, methyl fumarate, ethyl fumarate, propyl fumarate, butyl fumarate, and octyl fumarate are preferable, and acrylic acid and methacrylic acid are particularly preferable.
• a multifunctional monomer having two or more double bonds may be used as a monomer, as necessary.
• an aromatic divinyl compound such as divinyl benzene or divinyl naphthalene
• a diacrylate compound such as ethylene glycol diacrylate, 1,3-butylene glycol diacrylate, 1,4-butanediol diacrylate, 1,5-pentanediol diacrylate, 1, 6-hexanediol diacrylate, neopentyl glycol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyoxyethylene(2)-2,2-bis(4-hydroxyphenyl)propane diacrylate, or polyoxyethylene(4)-2,2-bis(4-hydroxyphenyl)propane diacrylate and a methacrylate compound thereof
• a multifunctional monomer such as pentaerythritol triacryl
• the ratio of these multifunctional monomers is preferably ⁇ 0.5 mass-% with respect to 100 mass-% of other monomers in a vinyl resin containing a carboxy group.
• a crosslinked body produced by a reaction of a carboxy group with a glycidyl group described below is hardly cut when the toner is manufactured, by setting the ratio to ⁇ 0.5 mass-%.
• the carboxy group-containing vinyl resin (C) As a method of manufacturing the carboxy group-containing vinyl resin (C), a well-known polymerization method such as solution polymerization, mass polymerization, suspension polymerization, or emulsion polymerization and a combination thereof can be employed, however, solution polymerization is suitably employed in terms of adjustment of the molecular weight distribution, mixing properties of the high molecular weight vinyl resin (H) and the low molecular weight vinyl resin (L) described below, and convenience of distribution adjustment of a carboxy group and a glycidyl group.
• a well-known polymerization method such as solution polymerization, mass polymerization, suspension polymerization, or emulsion polymerization and a combination thereof can be employed, however, solution polymerization is suitably employed in terms of adjustment of the molecular weight distribution, mixing properties of the high molecular weight vinyl resin (H) and the low molecular weight vinyl resin (L) described below, and convenience of distribution adjustment of a carboxy group and a
• carboxy group-containing vinyl resin (C) in the present invention by respectively polymerizing the high molecular weight vinyl resin (H) and the low molecular weight vinyl resin (L) alone in advance and then mixing them in a melted state or a solution state.
• carboxy group-containing vinyl resin (C) by polymerizing one of the high molecular weight vinyl resin (H) or the low molecular weight vinyl resin (L) alone, and then polymerizing the other vinyl resin in the presence of the former vinyl resin.
• an aromatic hydrocarbon such as benzene, toluene, ethylbenzene, xylene, or cumene is included, these are used alone or as a mixture thereof, and, xylene is preferable.
• the polymerization may be performed by using a polymerization initiator or so-called thermal polymerization may be performed without using a polymerization initiator.
• a polymerization initiator a polymerization initiator capable of being used as a radical polymerization initiator can be usually used.
• an azo-based initiator such as 2,2'-azobisisobutyronitrile, 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile), dimethyl-2,2'-azobisisobutyrate, 1,1'-azobis(1-cyclohexanecarbonitrile), 2-(carbamoylazo)-isobutyronitrile, 2,2'-azobis(2,4,4-trimethylpentane), 2-phenylazo-2,4-dimethyl-4-methoxyvaleronitrile, or 2,2'-azobis(2-methyl-propane), ketone peroxides such as methylethylketone peroxide, acetylacetone peroxide, or cyclohexanone peroxide, peroxy ketals such as 1,1-bis(t-butylperoxy)-3,3,5-trimethylcyclohexane, 1,1-bis(butylperoxy)cyclohexane,
• the type and the amount of the polymerization initiator can be appropriately selected to be used, depending on the e.g. the reaction temperature and the concentration of the monomer, and 0.01-10 pbm of the polymerization initiator is usually used with respect to 100 pbm of the monomer which is used.
• the carboxy group-containing vinyl resin (C) may further include at least one kind selected from a block copolymer consisting of a block consisting of a sequence of a constitutional unit derived from ethylene-based hydrocarbon and/or conjugated diene-based hydrocarbon and a block consisting of a sequence derived from styrene, and a hydrogen additive thereof, that is, a hydrogen additive block copolymer.
• the content of the block copolymer and the hydrogen additive block copolymer is preferably 0.05-1.5 pbm and more preferably 0.1-1.0 pbm, with respect to 100 pbm of the carboxy group-containing vinyl resin (C). It is possible to disperse a releasing agent in the binder resin without deteriorating storage stability and fluidity of the toner by setting the content to within the range described above. In doing so, it becomes easier to obtain the toner excellent in contamination resistance of a photoreceptor.
• ethylene-based hydrocarbon such as ethylene, propylene, 1-butene, 2-butene, isobutylene, 1-pentene, 2-pentene, 2-methyl-1-butene, 3-methyl-1-butene, 2-methyl-2-butene, 1-hexene, or 2,3-dimethyl-2-butene and conjugated diene-based hydrocarbon such as butadiene or isoprene may generally be used.
• ethylene-based hydrocarbon such as ethylene, propylene, 1-butene, 2-butene, isobutylene
• 1-pentene 2-pentene
• 2-methyl-1-butene 3-methyl-1-butene
• 2-methyl-2-butene 1-hexene
• 2,3-dimethyl-2-butene and conjugated diene-based hydrocarbon such as butadiene or isoprene
• block copolymers are manufactured, for example, by a method of using a reactive group in the block copolymer produced by a well-known living anion polymerization or living cation polymerization using these, and then blocking this reactive group with styrene.
• the method of manufacturing is not limited thereto and one which is manufactured by another well-known method of manufacturing in the related art may be used.
• Kraton a styrene-ethylene/butylene-styrene-based block copolymer (SEBS), a styrene-butadiene-styrene-based block copolymer, a styrene-isoprene-styrene-based block copolymer, a styrene-ethylene/propylene-styrene-based block copolymer, or a styrene-ethylene/propylene-based block copolymer) manufactured by Kraton Performance Polymers, Inc., SEPTON (a styrene-ethylene/propylene-based block copolymer or a hydrogenerated substance of a styrene-isoprene-based block copolymer) manufactured by KURARAY CO., LTD., and Tufprene (a styrene-butadiene-based block copolymer) manufactured by Kraton Performance Polymers, Inc
• the acid value of the carboxy group-containing vinyl resin (C) is preferably 5-30 mgKOH/g.
• the acid value is more preferably 10-25 mgKOH/g and further preferably 15-20 mgKOH/g.
• the reaction with the glycidyl group-containing vinyl resin (E) described below sufficiently proceeds, and as a result, it is possible to obtain the toner having more excellent offset resistance.
• the acid value is set to ⁇ 30 mgKOH/g, a carboxyl group-containing monomer becomes hardly unevenly distributed in the resin and thus the composition in the resin hardly becomes nonuniform. As a result, the toner becomes a toner having more excellent durability.
• the acid value refers to the number of mg of potassium hydroxide that is required to neutralize 1 g of a resin.
• the THF soluble content preferably have a peak in a region in which the molecular weight is preferably 2.5 ⁇ 10 4 to 1.2 ⁇ 10 5 in the molecular weight distribution measured by GPC, and it is preferable for the THF soluble content to have a peak in which the molecular weight is more preferably 3 ⁇ 10 4 to 1 ⁇ 10 5 in order to realize an excellent balance of fixing properties, offset resistance, and durability.
• the peak molecular weight By setting the peak molecular weight to ⁇ 2.5 ⁇ 10 4 , the strength of the resin is enhanced, and thus it is possible to obtain the toner having more excellent durability.
• the crosslinking formation sufficiently proceeds in the formation of a crosslinked body by the reaction with a glycidyl group described below, it is possible to obtain the toner having excellent offset resistance.
• the peak molecular weight to ⁇ 1.2 ⁇ 10 5
• the viscosity of the toner when fixed hardly increases, and thus it is possible to obtain the toner having more excellent fixing properties.
• the strength of the resin also becomes moderate, and thus it is possible to produce the toner having more excellent productivity.
• the acid value (AVH) of the high molecular weight vinyl resin (H) is 15-35 mgKOH/g and more preferably 19-27 mgKOH/g, in terms of fixing properties and offset resistance of the toner.
• the acid value is ⁇ 15 mgKOH/g
• the high molecular weight vinyl resin (H) easily reacts with the glycidyl group-containing vinyl resin described below and it is possible to produce the toner having more excellent offset resistance.
• the acid value is ⁇ 35 mgKOH/g
• an excessive crosslinking reaction with the glycidyl group-containing vinyl resin is suppressed, and as a result, the loss modulus in the fixing temperature range of the toner becomes moderate, and thus it is possible to produce the toner having more excellent fixing properties.
• the high molecular weight vinyl resin (H) may not necessarily be a single polymer, and two or more kinds of high molecular weight vinyl resins may be used. In this case, the high molecular weight vinyl resin (H) preferably satisfies the characteristics described above as a whole. In addition, when the single polymer is produced, it is also possible to add the carboxyl group-containing monomer during the polymerization or add separately at the beginning and end of polymerization.
• the THF soluble content preferably has a peak in which the molecular weight is 2 ⁇ 10 3 to 2 ⁇ 10 4 in the molecular weight distribution measured by GPC, and it is more preferable for the THF soluble content to have a peak in which the molecular weight is 4 ⁇ 10 3 to 1.6 ⁇ 10 4 from the viewpoint of fixing properties, durability, and productivity of the toner.
• the peak molecular weight By setting the peak molecular weight to ⁇ 2 ⁇ 10 3 , it is possible to produce the toner having more excellent durability.
• By setting the peak molecular weight to ⁇ 2 ⁇ 10 4 it is possible to obtain the toner having more excellent fixing properties and productivity.
• the acid value (AVL) of the low molecular weight vinyl resin (L) is preferably 1-10 mgKOH/g, and is more preferably 2-8 mgKOH/g in order to exhibit excellent fixing performance and offset resistance performance.
• the acid value (AVL) of the low molecular weight vinyl resin (L) is preferably 1-10 mgKOH/g, and is more preferably 2-8 mgKOH/g in order to exhibit excellent fixing performance and offset resistance performance.
• the low molecular weight vinyl resin (L) may not necessarily be a single polymer, and two or more kinds of low molecular weight vinyl resins may be used. At this time, the low molecular weight vinyl resin (L) preferably satisfies the characteristics described above as a whole. In addition, when the single polymer is produced, it is also possible to add the carboxyl group-containing monomer during the polymerization or add separately at the beginning and end of polymerization.
• the glycidyl group-containing vinyl resin (E) in the present invention can be obtained by using a well-known polymerization method using at least one kind of styrene-based monomer or acryl-based monomer (also including a methacryl-based monomer) and at least one kind of glycidyl group-containing monomer.
• the monomer exemplified in the explanation of the carboxy group-containing vinyl resin (C) is suitable.
• glycidyl acrylate, ⁇ -methyl glycidyl acrylate, glycidyl methacrylate, or ⁇ -methyl glycidyl methacrylate are suitable and glycidyl methacrylate and ⁇ -methyl glycidyl methacrylate are preferable.
• the THF soluble content has a peak in a range in which the molecular weight is preferably 3 ⁇ 10 4 to 7 ⁇ 10 4 and more preferably 4 ⁇ 10 4 to 6 ⁇ 10 4 in the molecular weight distribution measured by GPC.
• the epoxy value is set preferably to 0.003-0.100 Eq/100g and more preferably to 0.005-0.060 Eq/100g.
• the epoxy value refers to the number of moles of an epoxy group that exists in 100 g of a resin, and the measurement can be performed in accordance with JIS K-7236.
• the glycidyl group-containing vinyl resin (E) may not necessarily be a single polymer and two or more kinds of glycidyl group-containing vinyl resins may be used. In this case, the glycidyl group-containing vinyl resin (E) preferably satisfies the characteristics described above as a whole. In addition, when the single polymer is produced, it is also possible to add the glycidyl group-containing monomer during the polymerization or add separately at the beginning and end of polymerization.
• the binder resin for toner in the present invention includes a crosslinked component produced by the reaction of a carboxy group derived from the carboxy group-containing vinyl resin (C) with a glycidyl group derived from the glycidyl group-containing vinyl resin (E), and includes the THF insoluble component derived therefrom. It is more preferable that the THF insoluble component is preferably 10-40 mass-%, more preferably 15-30 mass-%, and further preferably 20-25 mass-% in the binder resin, from the viewpoint of an excellent balance among fixing properties, offset resistance, durability, and toner productivity.
• the THF insoluble component By setting the THF insoluble component to ⁇ 10 mass-%, it is possible to produce the toner having more excellent offset resistance, and furthermore, when a toner member such as a releasing agent, a charge controlling agent, a coloring agent, or a magnetic powder and the binder resin in the present invention are kneaded and pulverized to produce the toner, a sufficient shear at kneading is applied, the dispersion of the toner member becomes excellent, the electrification is uniformized, a decrease in environmental stability performance is suppressed, and thus it is possible to obtain an excellent development performance.
• a toner member such as a releasing agent, a charge controlling agent, a coloring agent, or a magnetic powder and the binder resin in the present invention are kneaded and pulverized to produce the toner, a sufficient shear at kneading is applied, the dispersion of the toner member becomes excellent, the electrification is uniformized, a decrease in environmental
• the toner having more excellent fixing performance is obtained and the low molecular weight component and the crosslinked body are prevented from being excessively separated, and thus the offset resistance is further improved.
• the toner does not become hard, it is possible to enhance the productivity of the toner.
• the minimum value (G' min ) of a storage elastic modulus (G') is preferably 0.2 ⁇ 10 4 Pa to 2.0 ⁇ 10 4 Pa in a temperature range of 150-200°C at a measurement frequency of 6.28 radian/second, and furthermore, is more preferably 0.4 ⁇ 10 4 Pa to 1.5 ⁇ 10 4 Pa from the viewpoint of a balance among fixing properties, offset resistance, and durability.
• the glass transition temperature (Tg) measured by DSC of the binder resin in the present invention is preferably 45-65°C, and more preferably 5-60°C from the viewpoint of low-temperature fixing properties and storage stability.
• Tg glass transition temperature
• the preferred binder resin used in the present invention contains at least the carboxy group-containing vinyl resin (C) and the glycidyl group-containing vinyl resin (E), and the ratio (C/E) of the carboxy group-containing vinyl resin (C) to the glycidyl group-containing vinyl resin (E) is 87/15 to 99/1 and preferably 90/10 to 97/5 as a mass ratio, from the viewpoint of offset resistance.
• the ratio of the glycidyl group-containing vinyl resin (E) By setting the ratio of the glycidyl group-containing vinyl resin (E) to ⁇ 15 mass-%, it is possible to produce the toner having more excellent offset resistance.
• a method of reacting the carboxy group-containing vinyl resin (C) with the glycidyl group-containing vinyl resin (E) As a method of reacting the carboxy group-containing vinyl resin (C) with the glycidyl group-containing vinyl resin (E), a method of mixing the carboxy group-containing vinyl resin (C) and the glycidyl group-containing vinyl resin (E) in a melted state to be reacted in the presence of at least the fatty acid metal salt (M) is preferable from the viewpoint of offset resistance and durability.
• any well-known method in the related art for example, a method in which both resins are put into a reactor vessel with a mixer and heated to be reacted in a melted state or a method of reacting in the presence of a solvent and then removing a solvent can be employed, however, in particular, a method using a twin screw kneader is preferable.
• a temperature when melting and kneading, and reacting differs depending on the amount of a functional group and the molecular weight of the carboxy group-containing vinyl resin (C) and the glycidyl group-containing vinyl resin (E), however, the temperature is preferably in a range of 100-220°C, more preferably 120-200°C, and further preferably 130-200°C.
• the reaction temperature is preferably in a range of 100-220°C, more preferably 120-200°C, and further preferably 130-200°C.
• the reaction temperature By setting the reaction temperature to ⁇ 220°C, the crosslinked reaction is prevented from excessively proceeding, a phase separation of a crosslinked component and an uncrosslinked component is suppressed, and thus it is possible to obtain the toner excellent in offset resistance.
• the depolymerization is suppressed and it is possible to reduce fear in which a problem such as development maintenance characteristics or odor of the toner by the residual volatile matter in the binder resin occurs.
• a method of melting and kneading to be reacted using a twin screw kneader there is also a method of removing water and a volatile component by injecting water from an injection opening into a twin screw kneader and reducing the pressure from a decompression opening which is arranged on the exit side than an injection opening. Water is sufficiently mixed with the resin by this method, and a volatile component such as a monomer or a solvent remained in the resin becomes easier to be removed when reducing the pressure.
• the binder resin for toner by cooling down and pulverizing the resin thus obtained.
• any well-known method in the related art can also be employed.
• a method of cooling down it is also possible to rapidly cool down by using, for example, a steel belt cooler.
• Another aspect in the present invention is a toner including the binder resin for toner and a coloring agent.
• a coloring agent a well-known pigment and dye in the related art can be used.
• a pigment for example, Mineral Fast Yellow, Navel Yellow, Naphthol Yellow S, Hansa Yellow G, Permanent Yellow NCG, Tartrazine Lake, Molybdenum Orange, Permanent Orange GTR, Pyrazolone Orange, Benzidine Orange G, Permanent Red 4R, Watching Red Calcium Salt, Eosine Lake, Brilliant Carmine 3B, Manganese Violet, Fast Violet B, Methyl Violet Lake, Cobalt Blue, Alkali Blue Lake, Victoria Blue Lake, Phthalocyanine Blue, Fast Sky Blue, Indanthrene Blue BC, Chrome Green, Pigment Green B, Malachite Green Lake, and Final Yellow Green G are included.
• a coloring pigment for magenta C.I.
• a coloring pigment for cyan examples of a coloring pigment for cyan, C.I. Pigment Blue 2, 3, 15, 15:1, 15:2, 15:3, 16, and 17, C.I. Acid Blue 6, C.I.
• Acid Blue 45 and a copper phthalocyanine pigment in which a phthalocyanine skeleton is substituted with 1-5 phthalimidomethyl groups are included.
• a coloring pigment for yellow C.I. Pigment Yellow 1, 2, 3, 4, 5, 6, 7, 10, 11, 12, 13, 14, 15, 16, 17, 23, 65, 73, 74, 83, 93, 97, 155, 180, and 185, C.I. and Vat Yellow 1, 3, and 20 are included.
• black pigment carbon black such as furnace black, channel black, acetylene black, thermal black, or lamp black are included.
• a dye C.I. Direct Red 1, C.I. Direct Red 4, C.I. Acid Red 1, C.I. Basic Red 1, C.I.
• Mordant Red 30 C.I. Direct Blue 1, C.I. Direct Blue 2, C.I. Acid Blue 9, C.I. Acid Blue 15, C.I. Basic Blue 3, C.I. Basic Blue 5, C.I. Mordant Blue 7, C.I. Direct Green 6, C.I. Basic Green 4, C.I. Basic Green 6, and Solvent Yellow 162 are included.
• coloring agents may be used alone or may be use in combination of two or more kinds thereof.
• the content of the coloring agent in the toner is preferably 0.05-20 pbm, more preferably 0.1-15 pbm, and further preferably 0.2-10 pbm, with respect to 100 pbm of the binder resin.
• a magnetic body can also be used as a substitute for these coloring agents.
• a metallic oxide including an element such as iron, cobalt, nickel, copper, magnesium, manganese, aluminum, or silicon are included, and specifically, triiron tetraoxide, diiron trioxide, zinc iron oxide, yttrium iron oxide, cadmium iron oxide, gadolinium iron oxide, copper iron oxide, lead iron oxide, nickel iron oxide, neodymium iron oxide, barium iron oxide, magnesium iron oxide, manganese iron oxide, lanthanum iron oxide, an iron powder, a cobalt powder, and a nickel powder are included. These magnetic materials may be used in combination of two or more kinds thereof, as necessary.
• a shape thereof it is preferable to use one in spherical shape, octahedron, or hexahedron, and furthermore, it is preferable to use one in spherical shape in terms of uniformly dispersing the magnetic powder in the toner.
• a BET specific surface area of the magnetic powder by a nitrogen adsorption method is 1-30 m 2 /g and it is more preferable to use one in which that of the magnetic powder is 2-20 m 2 /g, and furthermore, it is preferable to use the magnetic powder in which a Mohs hardness is 4-8.
• the average particle diameter of the magnetic body is preferably 0.01-0.8 ⁇ m, and more preferably 0.05-0.5 ⁇ m.
• the saturation magnetization is 50-200 Am 2 /kg, and the residual magnetization is 1-20 Am 2 /kg is preferable.
• the content of the magnetic body is preferably 4-200 pbm, more preferably 10-170 pbm, and further preferably 20-150 pbm, with respect to 100 pbm of the binder resin.
• the toner in the present invention may be used by partially adding as necessary, for example, polyvinyl chloride, polyvinyl acetate, polyester, polyvinyl butyral, polyurethane, polyamide, polystyrene, a rosin, a polymerized rosin, a modified rosin, a terpene resin, a phenol resin, an aromatic petroleum resin, a vinyl chloride resin, a styrene-butadiene resin, a styrene-(meth)acrylic copolymer, a chromane-indene resin, or a melamine resin, in a range in which an effect of the present invention is not hindered.
• a crystalline resin such as crystalline polyester having a melting point of 50-150°C can also be added.
• a method in which the coloring agent is dispersed in the binder resin or these raw material resins in advance, that is, a master batch is manufactured and these are added to the toner may be performed.
• 20-60 mass-% of the coloring agent and 80-40 mass-% of the resin component are mixed in a powder state, one in which the obtained mixture is kneaded by, for example, a twin screw kneader, an open roll kneader, or a batch type kneader such as a pressure kneader and then it is pulverized, may be used when the toner is manufactured.
• the toner in the present invention preferably includes a releasing agent in order to exhibit excellent fixing performance and offset resistance performance.
• aliphatic hydrocarbon-based wax such as low molecular weight polyethylene, low molecular weight polypropylene, a polyolefin copolymer, polyolefin wax, paraffin wax, microcrystalline wax, or Fischer-Tropsch wax; an oxide of aliphatic hydrocarbon-based wax such as polyethylene oxide wax; vegetable-based wax such as candelilla wax, carnauba wax, Japan wax, rice wax, or jojoba wax; animal-based wax such as bee wax, lanoline, or whale wax; mineral-based wax such as ozokerite, ceresine, or petrolatum; wax mainly containing fatty acid ester such as montanic acid ester or castor wax; wax in which fatty acid ester such as deacidified carnauba wax is partially or entirely deacidified; linear saturated fatty acid such as palmitic acid, stearic acid, montanic acid, or long
• wax having a functional group such as a hydroxyl group, an ester group, or a carboxyl group
• the wax is obtained by liquid-phase oxidation of a higher aliphatic hydrocarbon having one or more double bonds obtained by an ethylene polymerization method or an olefination method by thermally decomposing an petroleum-based hydrocarbon, an n-paraffin mixture obtained from a petroleum fraction, polyethylene wax obtained by an ethylene polymerization method, or a higher aliphatic hydrocarbon obtained by a Fischer-Tropsch synthesis method, by using a molecular oxygen-containing gas in the presence of boric acid and anhydrous boric acid.
• releasing agents may be used alone or may be used in combination of two or more kinds thereof.
• these releasing agents can be added in a step of manufacturing the high molecular weight vinyl resin (H), the low molecular weight vinyl resin (L), the carboxy group-containing vinyl resin (C), and the glycidyl group-containing vinyl resin (E), in a step of reacting the carboxy group-containing vinyl resin (C) with the glycidyl group-containing vinyl resin (E), or separately in respective steps.
• these addition methods are not limited, the releasing agent can be add by the method described above or a combination thereof, and further as necessary, the releasing agent can also be added when the toner is manufactured.
• the content of the releasing agent is preferably 1-10 pbm with respect to the total amount of 100 pbm of the carboxy group-containing vinyl resin (C), the glycidyl group-containing vinyl resin (E), and a reactant thereof, and furthermore, it is more preferable that the content of the releasing agent be 2-8 pbm from the viewpoint of a balance between offset resistance and storage stability. It is possible to produce the toner having more excellent offset resistance by setting the content of the releasing agent to ⁇ 1 pbm, and it is possible to suppress the deterioration of storage stability or the deterioration of contamination resistance of a photoreceptor by setting the content of the releasing agent to ⁇ 10 pbm. In addition, since the releasing agent becomes hardly unevenly distributed, separating the releasing agent from the toner is suppressed, and thus it is possible to produce the toner having more excellent durability.
• the toner in the present invention preferably includes a charge controlling agent in order to retain a positive electrostatic charging property or a negative electrostatic charging property.
• a charge controlling agent a well-known one in the related art can be used and these may be used as one kind or may be used in combination of two or more kinds thereof.
• a metal-containing azo dye is included as a charge controlling agent, it is possible to make the rising of the charge amount fast, and it is therefore preferable.
• the metal-containing azo dye is not particularly limited and it is possible to appropriately select the metal-containing azo dye in accordance to a purpose, however, for example, a chromium-containing monoazo dye, a cobalt-containing monoazo dye, an iron-containing monoazo dye, or a combination thereof can be used.
• the content of the charge controlling agent in the toner is preferably 0.05-10 pbm, more preferably 0.1-5 pbm, and further preferably 0.2-3 pbm, with respect to 100 pbm of the binder resin, in terms of a balance between the charge amount and fluidity of the toner.
• a method of adding inside the toner a method of externally adding, or a combination thereof can be applied.
• the surface treatment agent preferably exists between the toner and a carrier or between the toners.
• the powder fluidity, storage stability, electrification stability, and environmental stability can be improved and it is also possible to further improve a lifetime of a developer, by adding the surface treatment agent.
• a surface treatment agent a well-known one in the related art can be used.
• a fine silica powder, a fine titanium oxide powder, and a hydrophobic substance thereof are included.
• a fine silica powder a wet silica, a dry silica, and a complex of a dry silica and a metal oxide can be used, and furthermore, one in which these are subjected to a hydrophobic treatment with e.g. an organic silicon compound can be used.
• a hydrophobic treatment for example, a method of treating a fine silica powder produced by a vapor phase oxidation of a silicon halogenated compound with a silane compound and then treating with an organic silicon compound is included.
• silane compound used in a hydrophobic treatment for example, hexamethyl disilazane, trimethyl silane, trimethyl chlorosilane, trimethyl ethoxysilane, dimethyl dichlorosilane, methyl trichlorosilane, allyldimethyl chlorosilane, allylphenyl dichlorosilane, benzyldimethyl chlorosilane, bromomethyl dimethylchlorosilane, ⁇ -chloroethyl trichlorosilane, ⁇ -chloroethyl trichlorosilane, chloromethyl dimethylchlorosilane, triorganosilyl mercaptan, trimethylsilyl mercaptan, triorganosilyl acrylate, vinyldimethyl acetoxysilane, dimethyldiethoxy silane, dimethyldimethoxy silane, diphenyldiethoxy silane, hexamethyl disiloxane
• silicone oils such as dimethyl silicone oil, methylphenyl silicone oil, ⁇ -methyl styrene-modified silicone oil, chlorophenyl silicone oil, or fluorine-modified silicone oil are included.
• silicone oils such as dimethyl silicone oil, methylphenyl silicone oil, ⁇ -methyl styrene-modified silicone oil, chlorophenyl silicone oil, or fluorine-modified silicone oil are included.
• fine particles of a vinyl resin of 0.03-1 ⁇ m may also be used.
• a lubricant such as polyethylene fluoride, zinc stearate, or polyvinylidene fluoride, an abrading agent such as cerium oxide, silicon carbide, strontium titanate, a magnetic powder, or alumina, a conductivity imparting agent such as carbon black, zinc oxide, antimony oxide, or tin oxide may also be used.
• a shape of the surface treatment agent various shapes such as a particle having a small particle diameter in which the particle diameter is ⁇ 100 nm, a particle having a large particle diameter in which the particle diameter is ⁇ 100 nm, octahedron shape, hexahedron shape, needle shape, or fiber shape may be used.
• the surface treatment agent may be used alone or may be used in combination of two or more kinds thereof.
• the content of the surface treatment agent is preferably 0.1-10 mass-%, more preferably 0.1-5 mass-%, with respect to the entire toner.
• the toner in the present invention is used as a two component developer
• a well-known one in the relater art can be used as a carrier.
• particles consisting of a metal such as surface-oxidated iron or non-oxidated iron, cobalt, manganese, chromium, copper, zinc, nickel, magnesium, lithium, or rare earthes, and an alloy or an oxide thereof and having the number average particle diameter of 15-300 ⁇ m can be used.
• these carriers one in which the surface thereof is coated with a styrene-based resin, an acrylic-based resin, a silicone-based resin, a polyester resin, or a fluorine-based resin may be used.
• a magnetic carrier having a magnetic fine particle dispersion type core formed by dispersing magnetic fine particles in the resin and a coating layer including a coating resin which coats the surface of the magnetic fine particle dispersion type core may be used.
• the toner obtained by the present invention can be used in well-known various developing processes. For example, there is no limitation, however, a cascade development method, a magnetic brush method, a powder cloud method, a touch-down development method, a so-called micro-toning method using a magnetic toner manufactured by a grinding method as a carrier, and a so-called bipolar magnetic toner method obtained the required toner charge by a frictional electrification between the magnetic toners are included.
• the toner obtained by the present invention can also be used in various well-known cleaning methods in the related art such as a fur brush method or a blade method.
• the toner obtained by the present invention can be used in various well-known fixing methods in the related art.
• an oil less heat roll method, an oil application heat roll method, a thermal belt fixing method, a flash method, an oven method, and a pressure fixing method are exemplified.
• the toner obtained by the present invention may be used in a fixing device in which an electromagnetic induction heating system is employed.
• the toner obtained by the present invention may be used in an image forming method having an intermediate transfer step.
• the binder resin for toner obtained by the present invention and the toner including the same, there is provided the binder resin for toner having a more excellent balance among fixing properties, offset resistance, and durability.
• the toner in the present invention is manufactured by a well-known method in the related art using at least the coloring agent and the binder resin for toner in the present invention.
• a powder mixer such as a Henschel mixer
• each constituent component is sufficiently mixed by melting and kneading using a kneader such as a twin screw kneader or an open roll kneader.
• the toner may be subjected to, for example, a spheroidizing treatment by a surface treatment device, as necessary.
• a method of the surface treatment for example, a method of spheroidizing the toner by being flown into the high temperature air jet flow or a method of rounding off the corners of the toner by a mechanical impact is included, and for the purpose of e.g. improving the image quality, these surface treatments are performed and the average circularity measured by a flow type particle image measurement device (for example, manufactured by Sysmex Corporation, FPIA-3000) may be adjusted to ⁇ 0.960.
• a flow type particle image measurement device for example, manufactured by Sysmex Corporation, FPIA-3000
• a measuring method and a judging method of data are as follows. Furthermore, in Tables, St represents styrene, Mac represents methacrylic acid, BA represents n-butyl acrylate, and GMA represents glycidyl methacrylate.
• the acid value (AV) in the present Example was calculated as follows .
• Acid value mgKOH / g N / 10 KOH titration amount ml ⁇ F ⁇ 5.61 / Sample g ⁇ 0.01
• the peak molecular weight, the weight average molecular weight (Mw), the number average molecular weight (Mn), and the molecular weight distribution (Mw/Mn) in the present Example were determined by a GPC (gel permeation chromatography) method and are the conversion molecular weight in which a calibration curve is created by monodispersed standard polystyrene.
• the measurement conditions are as follows.
• the molecular weight of the main peak the weight average molecular weight (Mw), the number average molecular weight (Mn), and the molecular weight distribution (Mw/Mn) were determined as the molecular weight by the method described above.
• W is the amount of collected sample (g)
• B is the amount of the sodium hydroxide aqueous solution (ml) required for a blank test
• S is the amount of the sodium hydroxide aqueous solution (ml) required for the test for the sample
• N is the normality of the sodium hydroxide aqueous solution
• F is the titer of the sodium hydroxide aqueous solution.
• the viscoelasticity measurement in the present invention was determined by the following measurement.
• the THF insoluble content in the binder resin in the present invention was determined as follow.
• the unfixed image was fixed at a fixing speed of a heat roller of 190 mm/second at 130°C using a heat roller fixing device remodeled a fixing unit in a commercial copying machine.
• a load of 1.0 kgf was applied to the obtained fixed image by a sand eraser (manufactured by TOMBOW PENCIL CO., LTD.), the obtained fixed image was rubbed 6 times and the image density before and after the rubbing test was measured by a Macbeth type reflection densitometer.
• the image density after rubbing/the image density before rubbing ⁇ 100 was calculated as a fixing ratio and was determined by the following evaluation criteria.
• the heat roller fixing device used herein had no silicone oil supply mechanism.
• the environmental conditions were set to a normal temperature and normal pressure (temperature 22°C, relative humidity 55%).
• the evaluation of offset resistance was performed according to the measurement of evaluation of fixing properties described above. That is, the unfixed image was produced using the copying machine. Afterward, a fixing treatment was performed by the heat roller fixing device described above and whether a toner stain is generated at the non-image portion was observed. A state in which the preset temperature of a heat roller of the heat roller fixing device was risen from 100°C up to 250°C by sequentially 5°C was repeated and the width of the preset temperature in which the toner stain was not generated was set to the temperature width of offset resistance. In addition, an atmosphere of the copying machine was set to a temperature of 22°C and a relative humidity of 55%.
• Particle diameter change ratio the number median diameter D 50 before stirring ⁇ the number median diameter D 50 after stirring / the number median diameter D 50 before stirring ⁇ 100 was determined by the following criteria.
• the polymerization liquid was flashed at 160°C in a vessel under 1.33 kPa to remove e.g a solvent and a resin E-1 was obtained.
• the physical property values thereof are shown in Table 1.
• Table 1 (Glycidyl group-containing resin Crosslinked agent E) Name of resin Monomer composition Physical properties St BA Mac GMA Total Peak molecular weight Epoxy Value wt% wt% wt% wt% wt% wt% ⁇ 10 4 Eq/100 g E-1 76.0 19.0 0.0 5.0 100 5.1 0.035
• the carboxy group-containing vinyl resin (C), the glycidyl group-containing vinyl resin (E), and the fatty acid metal salt (M) were mixed so as to have the ratio described in Table 5.
• the content of the fatty acid metal salt (M) represents part by mass with respect to the total amount of 100 pbm of the carboxy group-containing vinyl resin (C) and the glycidyl group-containing vinyl resin (E).
• a toner T-22 was obtained in the same way as an example of manufacturing T-18, except adding 4.5 pbm of polyethylene wax (POLYWAX 725; manufactured by Baker Petrolite corporation) and 0.5 pbm of zinc stearate as a releasing agent.
• POLYWAX 725 polyethylene wax
• zinc stearate 0.5 pbm

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